JPH0325447B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polyether whose molecular chain ends are blocked with hydrolyzable silyl groups, which can be cured at room temperature into a rubber-like elastic body when exposed to moisture, and a method for producing the same, in particular a heat-resistant polyether. The present invention relates to a polyether useful as a base polymer for a room-temperature curable composition that provides a rubber-like cured product that has excellent hardness and weather resistance, has adhesive properties, and does not leave any sticky residue on the surface, and a method for producing the same. [Prior art and problems] Polymers having hydrolyzable silicon functional groups and whose main chain is polyether are known (Japanese Patent Application Laid-open No. 1983-1979).
156599, etc.). Room-temperature curable compositions based on this polymer have recently begun to be used as sealing materials for joints in buildings, joints in transportation machines, etc. (Japanese Unexamined Patent Publication No. 73998/1983, etc.). However, this type of polymer has poor heat resistance and weather resistance, so
There is a problem in that it is not suitable for use in locations that are relatively hot, such as joints in exterior walls of buildings that require weather resistance or parts of joints in transportation machinery. Furthermore, since this type of polymer does not inherently have adhesive properties, it is necessary to apply a primer treatment to the surface to which it is adhered before applying the sealant. Furthermore, since adhesiveness remains on the surface of the cured product,
There is a problem in that dust tends to adhere to the sealant. [Means for Solving the Problems] The present invention is intended to solve these problems. An object of the present invention is to provide a polyether whose molecular chain ends are blocked with a hydrolyzable silyl group, which is useful as a base polymer for a room-temperature curable composition that yields a rubber-like cured product free of silane, and a method for producing the same. That is, the present invention has the general formula: (In the formula, R ¹ and R ² are divalent hydrocarbon groups, A is a substituted or unsubstituted divalent aromatic group, and Z is

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[Formula] Indicates a group represented by the following, where R ³ has 1 to 1 carbon atoms.
6 alkyl group, R ⁴ is a monovalent hydrocarbon group, R ⁵ ,
R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups, R ⁶ , R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups,
R ¹³ is a monovalent hydrocarbon group, a is a number of 1 to 3, m is a number of 10 to 500, and n is a number of 1 or more. ) and has a molecular weight of 500 to 50,000, a polyether whose molecular chain ends are blocked with a hydrolyzable silyl group, and (A) a general formula; (In the formula, R ¹ and R ² are divalent hydrocarbon groups, m is 10
Indicates a number of ~500. ) Polyoxyalkylene (B) whose molecular chain terminal is blocked with an epoxy group General formula; H _z N-A-NH ₂ (wherein A represents a substituted or unsubstituted divalent aromatic group) ) and (C) general formula; (In the formula, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴
is a monovalent hydrocarbon group, a is a number from 1 to 3, and X is -
R ⁵ −NH ₂ , −R ⁶ −O−R ⁷ −NH ₂ , −R ⁸ −NH−R ⁹
−NH ₂ , −R ¹⁰ −S−R ¹¹ −NH ₂ or

[Formula] Indicates a group represented by the following formula, where R ⁵ , R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups, R ⁶ ,
R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups, R ¹³ is 1
represents a valent hydrocarbon group. ) A general formula characterized by reacting an amino group represented by the following with an organosilicon compound having a hydrolyzable group; (In the formula, R ¹ and R ² are divalent hydrocarbon groups, A is a substituted or unsubstituted divalent aromatic group, and Z is

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[expression] or

[Formula] Indicates a group represented by the following, where R ³ has 1 to 1 carbon atoms.
6 alkyl group, R ⁴ is a monovalent hydrocarbon group, R ⁵ ,
R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups, R ⁶ , R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups, R ¹³ is a monovalent hydrocarbon group, a is 1- 3, m is a number from 10 to 500, and n is a number of 1 or more. ), and has a molecular weight of 500 to 50,000, and relates to a method for producing a polyether whose molecular chain terminals are completely blocked with hydrolyzable silyl groups. General formula of the present invention; (In the formula, R ¹ , R ² , A, ^Z , m and n are as described above.) In the polyether represented by A system in which a unit and an oxypropylene unit are used in combination is preferable, and an oxypropylene unit is particularly preferable because it is easy to obtain raw materials and polymerize, and it is easy to maintain a liquid state even at a high degree of polymerization. The degree of polymerization m of oxyalkylene units is
If m is selected within the range of 10 to 500, it will be difficult to obtain a polyether that provides a rubber-like cured product with a sufficient elongation rate at a viscosity below that at which practical workability is obtained. On the other hand, if m is larger than 500, the heat resistance and weather resistance, which are the characteristics of the present invention, will decrease. The divalent hydrocarbon group of R ² is a methylene group,
Ethylene group, trimethylene group, tetramethylene group, phenylene group, cyclohexylene group and

Examples include groups represented by [Formula]. Among these groups, a methylene group is preferred from the viewpoint of easy availability of raw materials. A is a substituted or unsubstituted divalent aromatic group, and the raw materials are easily available, the compatibility with other raw materials is good, and the room-temperature curable composition using the polyether of the present invention has good construction workability,
and has a sufficient elongation rate, a phenylene group, a biphenylene group, or a group represented by the general formula: -R ¹⁴ -Q-R ¹⁵ - (wherein R ¹⁴ , R ¹⁵ and Q are as described above). It is preferable that there be. As a specific example of A,

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Examples include [Formula]. z is

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[Formula] (In the formula, R ³ to R ¹³ and a are as described above.) Here, the alkyl group having 1 to 6 carbon atoms in R ³ is
A methyl group or an ethyl group is preferred because the alkoxy group bonded to the silicon atom represented by R ³ O- has high hydrolyzability. The number a of hydrolyzable groups is 1
-3, but preferably a is 2 in order to obtain a polyether suitable as a base polymer for a composition that provides a rubber-like cured product with a high elongation rate. The monovalent hydrocarbon group for R ⁴ can be selected from alkyl groups, aryl groups, aralkyl groups, etc., but a methyl group is recommended from the viewpoint of ease of synthesis and raw material availability. R ⁵ , R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups. Also, R ⁶ , R ⁸ ,
R ¹⁰ and R ¹² are divalent hydrocarbon groups, and methylene, ethylene, trimethylene, and tetramethylene groups are preferred from the viewpoint of ease of synthesis of raw materials and precursors, and are preferred for chemical stability and ease of synthesis. A trimethylene group is particularly preferred from the viewpoint of safety considerations. On the other hand, as Z

[Formula] (In the formula, R ³ , R ⁴ , R ¹² , R ¹³ and a are as described above.) If heat resistance and weather resistance are important, R ¹³ may be selected from aryl groups. Preferred, R ¹³ if no surface tack residue is important
is preferably selected from an alkyl group or an alkenyl group. A specific example of such Z is etc. Further, n is a number of 1 or more, and may be 1, but if the molecular weight of the polyether of the present invention is 500 to 50,000
It is necessary to choose a range that is within the range of . When the polyether of the present invention is used as a base polymer for a sealant, if the molecular weight is less than 500, the elongation rate of the cured elastic body will not reach the elongation required for the sealant; Viscosity increases and workability decreases. The polyether of the present invention has, for example, (A) general formula; (In the formula, R ¹ , R ² and m are as described above.) Polyoxyalkylene (B) whose molecular chain terminal is blocked with an epoxy group General formula H _z N-A-NH ₂ (In the formula, A is as described above.) An aromatic diamine compound represented by: and (C) general formula; (In the formula, R ³ , R ⁴ and a are as described above,
X is −R ⁵ −NH ₂ , −R ⁶ −O−R ⁷ −NH ₂ , −R ⁸ −
NH−R ⁹ −NH ₂ , −R ¹⁰ −S−R ¹¹ −NH ₂ or

[Formula] is shown. However, R ⁵ to R ¹³ are as described above. ) It can be synthesized by reacting an amino group represented by the following with an organosilicon compound having a hydrolyzable group. A typical example of (A) is one obtained by adding epichlorohydrin to polyoxyethylene or polyoxypropylene, both ends of which are blocked with hydroxyl groups, in the presence of a basic catalyst or the like. (B) Specific examples of ingredients include:

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〔Effect of the invention〕

A sealing material can be obtained by adding a curing catalyst such as an organotin compound, a filler, and the like to the polyether of the present invention. By using the polyether of the present invention as a base polymer, it has excellent heat resistance and weather resistance, and exhibits adhesion without the need for brimer treatment on the surface to which it is applied.Also, since there is no residual surface tackiness, it is difficult to prevent dust from adhering to the surface. A sealing material that does not cause staining can be obtained. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples, Comparative Examples, and Reference Examples, all parts are by weight, and % is by weight. Example 1 For 0 epoxy equivalent of glycidyl group-end-blocked polyoxypropylene having an average degree of polymerization of 15, a molecular weight of about 1000, and a viscosity at 25°C of 270 cSt,

Methanol in an amount corresponding to 4 moles of [Formula] and 10% of polyoxypropylene was added, and heating and stirring was started at 60° C. under a nitrogen atmosphere. A portion was extracted at 4 hour intervals from the start of heating and stirring, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration.
The viscosity at 25°C was also measured. 16 hours after the start of heating and stirring, the titration of the epoxy group and the primary amine decreased by almost the theoretical amount, and the viscosity, which was 100cSt before the start of heating and stirring, reached 1500cSt.

Two moles of [Formula] were added, and heating and stirring was continued under the same conditions. A portion of the silane was sampled at 4-hour intervals after the addition of the silane, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration. almost disappeared,
Also, the peak due to protons of epoxide methylene by NMR (based on tetramethylsilane)
2.67 ppm) was no longer observed, so heating and stirring was stopped, and methanol was distilled off to form a pale yellow viscous liquid with a viscosity of 15,000 cSt at 25°C and a specific gravity of 1.01 at the same temperature (hydrolysis expressed by the following formula). Polyether whose molecular chain ends are blocked with a silyl group, P
-1) was obtained. An attempt was made to acetylate a small amount of the tertiary amine in a mixture of acetic anhydride and glacial acetic acid (9:1), and titrate the unacetylated tertiary amine with perchloric acid and glacial acetic acid using crystal violet as an indicator. Only a trace amount was observed. Further, the number average molecular weight measured by GPC (gel permeation chromatography) was 6200, and from this, the average structural formula of P-1 was estimated to be the following formula. Example 2 For 10 epoxy equivalents of glycidyl group-end-blocked polyoxypropylene with an average degree of polymerization of 32, a molecular weight of about 2000, and a viscosity at 25°C of 550 cSt,

Methanol in an amount corresponding to 4 moles of [Formula] and 10% of polyoxypropylene was added, and heating and stirring was started at 60° C. under a nitrogen atmosphere. A portion of the sample was extracted at 4 hour intervals from the start of heating and stirring, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration.
The viscosity at 25°C was measured. From the start of heating and stirring
After 16 hours, the titration of the epoxy group and the primary amine decreased by almost the theoretical amount, and the viscosity, which was 230 cSt before the start of heating and stirring, reached 3900 cSt. 2 mol of was added, and heating and stirring was continued under the same conditions. A portion of the silane was sampled at 4-hour intervals after the addition of the silane, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration. It almost disappeared, and the peak due to epoxide methylene protons was no longer observed by NMR, so heating and stirring was stopped, methanol was distilled off, and the temperature was heated to 25°C.
The viscosity at is 26000cSt, and the specific gravity at the same temperature is
A pale yellow viscous liquid of 1.01 (polyether whose molecular chain ends were blocked with a hydrolyzable silyl group represented by the following formula, P-2) was obtained. Incidentally, using a small amount of the tertiary amine, an attempt was made to titrate the tertiary amine in the same manner as in Example 1, but only a very small amount was observed. Furthermore, the number average molecular weight determined by GPC measurement was 11,200, and from this it was estimated that the average structural formula of P-2 was as follows. Example 3 For 6 epoxy equivalents of glycidyl group-terminated polyoxypropylene with an average degree of polymerization of 50, a molecular weight of about 3000, and a viscosity of 970 cSt at 25°C,

2 moles of [Formula] and methanol in an amount corresponding to 10% of polyoxypropylene were added, and heating and stirring was started at 60°C under a nitrogen atmosphere. A portion of the sample was taken out at 6 hour intervals from the start of heating and stirring, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration, and the viscosity at 25°C was also measured. 18 hours after the start of heating and stirring, the titration of the epoxy group and the primary amine decreased by almost the theoretical amount, and the viscosity, which was 390 cSt before the start of heating and stirring, reached 4100 cSt. 2 mol of was added and heating and stirring was continued under the same conditions. A portion of the silane was sampled at 4-hour intervals after the addition of the silane, and the total amount of epoxy groups and primary amines in the sample was determined using potentiometric titration. As the peak of epoxide methylene was almost completely disappeared and the peak of epoxide methylene was no longer observed by NMR, heating and stirring was stopped, methanol was distilled off, and the viscosity at 25℃ was reduced.
34000cSt, a pale yellow viscous liquid with a specific gravity of 1.01 at the same temperature (polyether whose molecular chain ends are blocked with hydrolyzable silyl groups represented by the following formula, P-
3) was obtained. In addition, using a small amount, Example 1
An attempt was made to titrate tertiary amine in the same manner as above, but only a very small amount was observed. Furthermore, the number average molecular weight determined by GPC measurement was 9000, and from this it was estimated that the average structural formula of P-3 was as follows. Example 4 For 10 epoxy equivalents of the same glycidyl group-terminated polyoxypropylene used in Example 2, 4 moles of the same diaminodiphenyl ether used in Example 2 and equivalent to 10% of the polyoxypropylene were added. The mixture was heated and stirred at 60° C. for 16 hours under the same conditions as in Example 2, that is, under a nitrogen atmosphere. Then,

2.2 mol of [Formula] was added, and heating and stirring was continued under the same conditions. After adding the above silane, a portion was taken out at 4 hour intervals and the peak due to protons of epoxide methylene was observed by NMR.
After 12 hours, the peak disappeared, so heating and stirring was stopped, and methanol was distilled off to form a pale yellow viscous liquid with a viscosity of 21,000 cSt at 25°C and a specific gravity of 1.01 at the same temperature (hydrolyzable liquid expressed by the following formula). Polyether whose molecular chain ends are blocked with silyl groups,
P-4) was obtained. Furthermore, the number average molecular weight determined by GPC measurement was 11,000, and from this it was estimated that the average structural formula of P-4 was the following formula. Example 5 For 10 epoxy equivalents of the same glycidyl group-terminated polyoxypropylene used in Example 1, 4 moles of diaminodiphenylmethane as used in Example 1 and equivalent to 10% of the polyoxypropylene were added. An amount of methanol was added thereto, and the mixture was heated and stirred at 60°C for 16 hours under the same conditions as in Example 1, that is, under a nitrogen atmosphere. then

3 mol of [Formula] was added, and heating and stirring was continued under the same conditions. A portion of the silane was extracted at 4-hour intervals after the above silane was added, and the epoxy groups in the sample were quantified using potentiometric titration. As a result, the epoxy groups in the sample almost disappeared 16 hours after the addition of the silane, and the protons of epoxide methylene were determined by NMR. Since the peak due to
The viscosity at is 12000cSt, and the specific gravity at the same temperature is
A viscous liquid (polyether P-5 whose molecular chain ends are blocked with a hydrolyzable silyl group represented by the following formula) with a molecular weight of 1.01 was obtained. Moreover, the number average molecular weight by CPC measurement was 7300, and from this it was estimated that the average structural formula of P-5 was the following formula. Reference Examples 1 to 5 Polyethers (P-1 to 5) whose molecular chain ends were blocked with hydrolyzable silyl groups obtained in Examples 1 to 5
To 100 parts, fillers, inorganic pigments, and thixotropic agents shown in Table 1 were added and dispersed uniformly with a triple roll, and then an organic tin compound also shown in Table 1 was added and mixed. , Samples-1 to 5
I got it. These samples were cured into sheets with a thickness of about 2 mm, cured at room temperature for 14 days, and then punched into JIS No. 2 dumbbells, and the surface conditions were observed by finger touch and a tensile test was performed. Next, the dumbbell-shaped sample piece obtained in the same manner was placed in a 150°C dryer and a weather meter, and after applying the deterioration conditions (heating and ultraviolet irradiation) for the period shown in Table 1, the condition of the sample piece was observed. A tensile test was conducted. These results are also shown in Table 1. Comparative example 1 Molecular weight approximately 8000, as a terminal group For 100 parts of polyoxypropylene with
After adding the filler, inorganic pigment, and thixotropic agent shown in Table 1 and uniformly dispersing them with a triple roll, the organic tin compound also shown in Table 1 was added and mixed to obtain Sample-6. Ta. Tests similar to those in Reference Examples 1 to 5 were conducted using Sample-6. The results are also shown in Table 1. Reference Examples 6-10 Same samples 1-5 as those prepared in Reference Examples 1-5
Using this, a shear adhesion test specimen shown in FIG. 1 was prepared. After curing the created test specimen at room temperature for 28 days,
A tensile test was conducted. The results are shown in Table 2. Comparative Example 2 Using the same sample 6 prepared in Comparative Example 1, a shear adhesion test specimen shown in FIG. 1 was prepared. The same tests as in Reference Examples 6 to 10 were conducted using this test specimen. The results are also shown in Table 2.

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【table】 [Brief explanation of drawings]

FIG. 1 shows a perspective view of a specimen subjected to a shear adhesion test. The unit in the figure is mm. 1... Sample, 2... Adherent (glass, aluminum and PVC steel plate).

Claims (1)

[Claims] 1. General formula; (In the formula, R ¹ and R ² are divalent hydrocarbon groups, A is a substituted or unsubstituted divalent aromatic group, and Z is [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] represents a group, where R ³ has 1 to 1 carbon atoms.
6 alkyl group, R ⁴ is a monovalent hydrocarbon group, R ⁵ ,
R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups, R ⁶ , R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups, R ¹³ is a monovalent hydrocarbon group, a is 1- 3, m is a number from 10 to 500, and n is a number of 1 or more. ) Polyether having a molecular weight of 500 to 50,000 and whose molecular chain ends are blocked with a hydrolyzable silyl group. 2. The polyether according to claim 1, wherein R ¹ is an ethylene group and/or a propylene group. 3. The polyether according to claim 2, wherein R ¹ is a propylene group. 4. The polyether according to claim 1, wherein R ² is a methylene group. 5. The polyether according to claim 1, wherein R ³ is a methyl group or an ethyl group. 6 A is a substituted or unsubstituted phenylene group, biphenylene group or general formula; -R ¹⁴ -Q-R ¹⁵ - (wherein R ¹⁴ and R ¹⁵ are substituted or unsubstituted phenylene group, Q is an alkylene group, - The polyether according to claim 1, which is a divalent aromatic group represented by O-, -S- or [Formula]. 7 Z is [Formula] [Formula] [Formula] or [Formula] (In the formula, R ³ to R ¹¹ and a are as described above.)
The polyether according to claim 1, which is 8. The polyether according to claim 1, wherein a is 2. 9 (A) General formula; (In the formula, R ¹ and R ² are divalent hydrocarbon groups, m is
Indicates a number from 10 to 500. ) A polyoxyalkylene whose molecular chain end is blocked with an epoxy group. (B) An aromatic diamine compound represented by the general formula: H _z N-A-NH ₂ (wherein A represents a substituted or unsubstituted divalent aromatic group). and (C) general formula; (In the formula, R ³ is an alkyl group having 1 to 6 carbon atoms,
R ⁴ is a monovalent hydrocarbon group, a is a number from 1 to 3, X
are −R ⁵ −NH ₂ , −R ⁶ −O−R ⁷ −NH ₂ , −R ⁸ −
NH-R ⁹ -NH ₂ , -R ¹⁰ -S-R ¹¹ -NH ₂ or a group represented by the formula, where R ⁵ , R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene. basis,
R ⁶ , R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups,
R ¹³ represents a monovalent hydrocarbon group. ) A general formula characterized by reacting an amino group represented by the following with an organosilicon compound having a hydrolyzable group; (In the formula, R ¹ and R ² are divalent hydrocarbon groups, A is a substituted or unsubstituted divalent aromatic group, and Z is [formula] [formula] [formula] [formula] or [formula] represents a group, where R ³ has 1 to 1 carbon atoms.
6 alkyl group, R ⁴ is a monovalent hydrocarbon group, R ⁵ ,
R ⁷ , R ⁹ and R ¹¹ are substituted or unsubstituted phenylene groups, R ⁶ , R ⁸ , R ¹⁰ and R ¹² are divalent hydrocarbon groups, R ¹³ is a monovalent hydrocarbon group, a is 1- 3, m is a number from 10 to 500, and n is a number of 1 or more. ) and has a molecular weight of 500 to 50,000, a method for producing a polyether whose molecular chain ends are blocked with a hydrolyzable silyl group.